[go: up one dir, main page]

EP3947484B1 - Polyoléfine ramifiée à longue chaîne trifonctionnelle - Google Patents

Polyoléfine ramifiée à longue chaîne trifonctionnelle Download PDF

Info

Publication number
EP3947484B1
EP3947484B1 EP20721035.2A EP20721035A EP3947484B1 EP 3947484 B1 EP3947484 B1 EP 3947484B1 EP 20721035 A EP20721035 A EP 20721035A EP 3947484 B1 EP3947484 B1 EP 3947484B1
Authority
EP
European Patent Office
Prior art keywords
polymer
diene
functional
tri
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP20721035.2A
Other languages
German (de)
English (en)
Other versions
EP3947484A1 (fr
Inventor
Robert D.J. FROESE
Teresita KASHYAP
Oscar D. Redwine
Daniel J. Arriola
Robert L. Sammler
Cornelis F.J. Den Doelder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP3947484A1 publication Critical patent/EP3947484A1/fr
Application granted granted Critical
Publication of EP3947484B1 publication Critical patent/EP3947484B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/64006—Bidentate ligand
    • C08F4/64041—Monoanionic ligand
    • C08F4/64044—NN
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/02—Low molecular weight, e.g. <100,000 Da.
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/09—Long chain branches

Definitions

  • Embodiments of the present disclosure generally relate to polymer compositions having tri-functional long-chain branches and the process by which the polymer compositions are synthesized.
  • Olefin based polymers such as polyethylene
  • Olefin based polymers are produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin based polymers.
  • Polyethylene and polypropylene are manufactured for a wide variety of articles.
  • the polyethylene and polypropylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties that render the various resins suitable for use in different applications.
  • the amount of long-chain branching in a polyolefin affects the physical properties of that polyolefin.
  • the effect of branching on properties of polyethylene depends on the length and the amount of branches. Short branches mainly influence the mechanical and thermal properties. As the branch length increases, the branches are able to form lamellar crystals that the mechanical and thermal properties diminish. Small amounts of long-chain branching can alter the polymer processing properties significantly.
  • long-chain branching a vinyl or terminal double bond of a polymer chain is incorporated into a new polymer chain.
  • Reincorporation of vinyl terminated polymers and introducing a diene comonomer are two mechanisms by which a vinyl group on a polymer strand is incorporated into a second polymer strand.
  • long-chain branching is induced via radicals. It is difficult to control the amount of branching in all three mechanisms. When using radicals or dienes to initiate long-chain branching, the branching may become too numerous, thereby causing gelling and reactor fouling.
  • the reincorporation mechanism does not produce much branching, and branching can only occur after the polymer strand is produced, thereby further limiting the amount of branching that can occur.
  • WO-A-96/12744 relates to a copolymer derived from at least three monomers comprising: a) one mono-olefin having a single Ziegler-Natta polymerizable bond; b) a second monomer having at least one Ziegler-Natta polymerizable bond; c) a third monomer having at least two Ziegler-Natta polymerizable bonds such monomer being: i) straight-chained and of less than six or at least seven carbon atoms; ii) other than straight-chained; or iii) combinations thereof, such copolymer having: d) at least one carbon-carbon unsaturated bond per number average molecule; e) viscous energy of activation (E a ) at least 1 kcal/mol greater than a copolymer having a linear backbone derived from some monomers, but excluding species having at least two Ziegler-Natta polymerizable bonds; f) crystallinity level in the range of 10%
  • Embodiments of this disclosure include polymers comprising the polymerized product of ethylene, at least one diene comonomer, and optionally at least one C 3 to C 14 comonomer.
  • the polymer comprises tri-functional long-chain branches resulting from the diene that occur at a frequency of at least 0.03 per 1000 carbon atoms of the polymer.
  • the diene has a structure according to formula (I):
  • X is SiR 2 or GeR 2 , wherein each R is independently C 1 -C 12 hydrocarbyl or -H. In some embodiments, X in formula (I) is -Si(R) 2 -, and wherein each R is C 1 -C 12 alkyl.
  • Various embodiments of the process include polymerizations that occur in a solution polymerization reactor or a particle forming polymerization reactor such as a slurry reactor or a gas phase reactor, wherein the molecular or solid-supported catalyst is delivered to the reaction media or developed in the reaction media, wherein the reactor system is batch or continuous or a hybrid such as semi-batch, wherein the reactor residence time distribution is narrow such as in non-backmixed reactors or broad such as in backmixed reactor and series and recycle reactors.
  • polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomers.
  • interpolymer refers to a polymer prepared by the polymerization of at least two different types of monomers.
  • the generic term interpolymer thus includes copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers.
  • Polyethylene or "ethylene-based polymer” shall mean polymers comprising greater than 50 mol% of units derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers).
  • Common forms of polyethylene known in the art include Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE); Very Low Density Polyethylene (VLDPE); single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m- LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).
  • LDPE Low Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • ULDPE Ultra Low Density Polyethylene
  • VLDPE Very Low Density Polyethylene
  • m- LLDPE linear low Density Polyethylene
  • MDPE Medium Density Polyethylene
  • HDPE High Dens
  • Ethylene-diene-based polymer shall mean polymers comprising greater than 50 mol% of units derived from ethylene monomer and also include a small component of diene.
  • the ethylene-diene-based polymer may optionally include units derived from one or more (C 3 -C 12 ) ⁇ -olefins.
  • Embodiments of this disclosure include polymers comprising the polymerized product of ethylene, at least one diene comonomer, and optionally at least one C 3 to C 14 comonomer.
  • the polymer comprises tri-functional long-chain branches resulting from the diene that occur at a frequency of at least 0.03 per 1000 carbon atoms of the polymer.
  • the diene has a structure according to formula (I):
  • X is SiR 2 or GeR 2 , wherein each R is independently C 1 -C 12 hydrocarbyl or -H. In some embodiments, X in formula (I) is -Si(R) 2 -, and wherein each R is C 1 -C 12 alkyl. In one or more embodiments, the diene is dimethyldivinylsilane.
  • R of formula (I) is C 1 -C 12 alkyl
  • the C 1 -C 12 alkyl is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl; 1-hexyl, 1-heptyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, or dodecyl.
  • C 1 -C 12 alkyl means a saturated straight or branched hydrocarbon radical of from 1 to 12 carbon atoms
  • the tri-functional long-chain branches of the polymer occur at a frequency of at least 0.05 per 1000 carbon atoms. In one or more embodiments, the tri-functional long-chain branches of the polymer occur at a frequency of at least 0.1 per 1000 carbon atoms. In various embodiments, the tri-functional long-chain branches of the polymer occur at a frequency of at least 0.2 per 1000 carbon atoms.
  • the polymers of this disclosure are produced via a process of synthesizing long-chain branched polymers.
  • the process includes contacting together one or more C 2 -C 14 alkene monomers, at least one diene, optionally a solvent, and a multi-chain catalyst optionally in the presence of hydrogen, wherein the multi-chain catalyst comprises a plurality of polymerization sites and wherein the diene has a structure according to formula (I).
  • At least two polymer chains of the C 2 -C 14 alkene monomers are produced, each polymer chain polymerizing at one of the polymerization sites.
  • the long-chain branched polymers are synthesized by connecting the two polymer chains with the diene.
  • the connecting or joining of the two polymer chains being performed in a concerted manner during the polymerization.
  • the long-chain branched polymers have a ratio of tri-functional to tetra-functional long chain branches from 0.05:1 to 100:0.
  • the ratio of tri-functional to tetra-functional long chain branches is adjusted if the ratio deviates from a target ratio of tri-functional to tetra-functional long chain branches.
  • the ratio is adjusted by altering an amount of C 2 -C 14 alkene monomer feed, an amount of hydrogen feed, or combinations thereof.
  • the long-chain branched polymers have a ratio of tri-functional to tetra-functional long chain branches from 0.05:1 to 100:0.
  • the tri-functional long chain branches are produced from the diene, wherein the tri-functional long chain branches occur at a frequency of at least 0.03 per 1000 carbon atoms.
  • connecting when in reference to “connecting two polymer chains” broadly means that the polymer chains are covalently linked.
  • the ratio of tri-functional to tetra-functional long chain branches is adjusted if the ratio deviates from a target ratio of tri-functional to tetra-functional long chain branches.
  • the ratio is adjusted by altering the amount of C 2 -C 14 alkene monomer feed, the amount of hydrogen feed, the ratio of C 2 -C 14 alkene monomer feed to hydrogen, or combinations thereof.
  • the molar feed ratio of C 2 -C 14 alkene monomer feed to hydrogen is from 100:0 to 1:1. In one or more embodiments, the feed ratio is from 80:1 to 25:1. In various embodiments, the feed ratio is from 70:1 to 30:1, from 60:2 to 10:1, or from 50:1 to 25.1.
  • the process of synthesizing polymers according to this disclosure is different from the conventional long-chain branching or prior "Ladder" branching, described in Application Nos. PCTUS2019/053524 ; PCTUS2019/053527 ; PCTUS2019/053529 ; and PCTUS2019/053537, each filed September 27, 2019 .
  • the term "long-chain branching” refers to branches having greater than 100 carbon atoms.
  • a “branch” refers to a portion of polymer that extends from a tertiary carbon atom. When the branch extends from a tertiary carbon atom, there are two other branches, which collectively could be the polymer strand from which the branch extends.
  • the branching is defined as tri-functional long-chain branching in that the branch point has three polymer chains emanating from it.
  • long-chain branching LCB
  • LCB long-chain branching
  • Naturally occurring LCB can occur through vinyl termination of the polymer chain and reinsertion of the macromolecular vinyl creating a tri-functional long-chain branch.
  • a variety of methods can either determine LCB, such as nuclear magnetic resonance (NMR), or distinguish the effect of LCB in the polymer.
  • LCB the effect of LCB is observed in shear flow in the van Gurp-Palmen analysis, also an increase of the shear viscosity at low angular frequencies and strength of the shear thinning behavior can be attributed to LCB.
  • extensional flow the influence of LCB is usually identified in the degree of strain hardening or the strength of the melt and the maximum deformation achieved.
  • a high level of natural LCB in a polymer is difficult to achieve due to the limited concentration of vinyl terminated polymers (maximum one per polymer chain) and the need to run to high ethylene conversion to ensure LCB formation. To ensure high conversion, there is a low ethylene concentration in the reactor, thus enabling a great amount of vinyl terminated polymers to be reinserted in a second polymer chain.
  • LCB There is minimal long-chain branching that forms through the naturally occurring branching.
  • One way to enhance LCB is through the addition of ⁇ , ⁇ -dienes to the polymerization system, whether it be in a radical, heterogeneous, or homogeneous process.
  • dienes add to the polymer chain in a similar manner to ⁇ -olefins, but leave a pendant vinyl group, which can insert into a polymer chain a second time to create the LCB, as illustrated by Scheme 2.
  • the diene length does not matter, only that it can link two polymer chains together.
  • the concentration of pendant vinyls can be controlled through the amount of diene added to the reactor.
  • the degree of LCB can be controlled by the concentration of pendant vinyls.
  • the conventional process of incorporating dienes into a polymer synthesis system suffers from the fundamental flaw of gel formation or reactor fouling.
  • the kinetic modeling discussed in later paragraphs, may provide good predictive results that enable a better understanding into gel formation.
  • longer polymer chains have more inserted olefins, thus more inserted dienes, thus more pendant vinyls, implying that longer polymer chains will be more likely to re-insert into the catalyst to form a LCB.
  • the longer polymer chains preferentially re-insert forming tetra-functional branches, which are even larger polymer molecules, and a gel problem results.
  • a tetra-functional LCB has a short segment (number of carbons between the two double bonds of the diene), which bridges two long chains on each side of the short segment.
  • M w weight average molecular weight
  • M n number average molecular weight
  • gel refers to a solid composed of at least two components: the first is a three dimensional cross-linked polymer and the second is a medium in which the polymer does not fully dissolve. When the polymer gels and does not fully dissolve, the reactor may become fouled with polymer gel.
  • Ladder Branched polymer refers to the polymer formed from the "Ladder Branching mechanism". As described in Scheme 2, the polymer has a tetra-functional long-chain branched structure. Additionally, the term “Ladder Branched” polymer and “Ladder Branching Mechanism” also refers to the tri-functional polymer and the polymerization processes that produce tri-functional long chain branched polymers.
  • the process to synthesize the tetra-functional long-chain branched polymer achieves long-chain branching and avoids gel formation or reactor fouling.
  • reactor fouling is avoided by reacting the two alkenes of the diene in a concerted fashion across two proximal polymer chains.
  • one alkene of the diene reacts before the second alkene, and the second alkene reacts before too many ethylene molecules are added to the polymer strand, thereby removing the close proximity the second alkene has to the reactive site.
  • the reaction of the first alkene of the diene into one polymer and second alkene of the diene into an adjacent polymer chain before many ethylene monomers are inserted is referred to as a concerted addition of the diene into proximal polymer chains.
  • Polymer strands are linear segments of a polymer, or more specifically a copolymer, which are optionally joined at the end(s) by branching junctures.
  • branching junctures For example, a tetra-functional branch juncture joins the ends of four polymer strands, as opposed to a tri-functional branch juncture, which joins the ends of three polymer strands as shown in Scheme 1.
  • a mechanism describes how a dual-chain catalyst can create a unique tri-functional bridged molecular architecture when polymerizing diene co-monomers under desired conditions.
  • the term "diene” refers to a monomer or molecule having two alkenes.
  • a pictorial description of the mechanism is shown in Scheme 5, in which the catalyst center produces two polyolefin chains.
  • Scheme 5 shows how a combination of diene bridging and chain transfer may create a diene "Ladder Branched" tri-functional polymer structure.
  • diene "Ladder Branched" polymer refers to the long-chain branching, in which a short chain or rung that includes one to twelve carbon atoms links two polymer chains together.
  • the metal-ligand catalyst having at least two polymer chain sites, propagates two separate polymer chains.
  • One alkene of the diene is incorporated into one of the sites of the catalyst, and it is believed that due to the close proximity of the propagation sites, the second alkene of the diene is then quickly incorporated into the second polymer chain, thereby forming a bridge or rung.
  • diene This successive addition of diene is referred to as a "concerted” addition of the diene, distinguishing it from catalysts without two proximal chains where diene addition leads to a concentration of vinyl containing polymers in the reactor, which react at a later time.
  • the term “rung” refers to the diene once it is incorporated into two separate polymer strands, thereby linking the strands together. The first and second polymer strands continue to propagate until the polymer transfers to another catalyst, the polymer is released from the catalyst, the catalyst dies, or another diene is added.
  • the tri-functional Ladder branching can occur upon the introduction of hydrogen gas.
  • the introduction of hydrogen gas terminates the polymer chain at one of the polymerization cites of the multi-chain catalyst. Upon termination, the polymer chain disconnects, thus yielding a tri-functional polymer.
  • the polymer of this disclosure includes tri-functional long chain branches that result from the diene of formula (I).
  • the ratio of tri-function to tetra-functional branches is controlled via adjusting the ethylene/hydrogen ratio in the reactor or other reactor conditions such as temperature. In some embodiments, the ratio of tri-functional to tetra-functional long chain branches is greater than 0.1:1 to about 100:0.
  • the molecular weight distribution (MWD) is defined by the weight average molecular weight divided by the number average molecular weight (M w /M n ).
  • MWD is defined by the weight average molecular weight divided by the number average molecular weight (M w /M n ).
  • MWD weight average molecular weight
  • M w weight average molecular weight
  • M n number average molecular weight
  • the combination of a multi-chain catalyst and diene influences the amount and type of branching.
  • Embodiments of the present disclosure are directed to controlling polymer properties such as: 1) the use of multiple diene species, 2) the use of multiple multi-chain catalyst species, 3) the combination of polymerization environments including multiple reactors zones or a gradient of zones, or 4) the control and combination of different types of long-chain branching, for example, tri-functional and tetra-functional long-chain branching.
  • long-chain branching refers to branches having greater than 100 carbon atoms.
  • branch refers to a portion of polymer that extends from a tertiary carbon atom. When the branch extends from a tertiary carbon atom, there are two other branches, which collectively could be the polymer chain from which the branch extends.
  • Long-chain branching may occur naturally in the polymerization process, as shown in Scheme 1. This may occur through termination of the polymer chain and reinsertion of the macromolecular vinyl creating a tri-functional long-chain branch.
  • the process for polymerizing the long-chain branched polymer includes a catalyst with at least two active sites in close proximity (multi-chain catalysts). Close proximity includes a distance of less than 8 angstroms ( ⁇ ), less than 6 ⁇ , or approximately 5 ⁇ .
  • the diene structure according to formula (I), where X is -C(R) 2 - (not encompassed by the wording of the claims), -Si(R) 2 -, or -Ge(R) 2 -, where each R is independently, a hydrogen or hydrocarbyl group, allows one to estimate the size of the diene.
  • the end-to-end distance of the diene according to formula (I), in which X is -Ge(R) 2 -, diene is approximately 7.5 ⁇ . Therefore, polymerization sites of the multi-chain may be within 8 ⁇ or in the case of bimetallic catalysts, the two metals to be within 8 ⁇ .
  • M/nm 2 surface concentration of metals which are often measured in metal atoms per nanometer squared (M/nm 2 ). This surface coverage provides an estimate of accessible metals on the surface which if evenly dispersed may be converted to an M-M distance, which reflects the distance between the polymer chains. For an extended surface, 1 metal/nm 2 leads to a distance of 10 ⁇ between the metal atoms. At 8 ⁇ , one can determine the coverage at 1.5 metal/nm 2 .
  • catalysts having at least two active sites, wherein the active sites are in close proximity include, but are not limited to: bimetallic transition metal catalysts; heterogeneous catalysts; dianionic activators with two associated active catalysts; a ligated transition metal catalyst with more than one propagating polymer chain; a group IV olefin polymerization catalyst including monoanionic groups, bidentate monoanionic groups, tridentate monoanionic groups, or a monodentate, bidentate, or tridentate monoanionic groups with external donors.
  • a mechanism describes how a dual-chain catalyst can create a unique tri-functional bridged molecular architecture when polymerizing diene co-monomers under desired conditions.
  • the term "diene” refers to a monomer or molecule having two alkenes.
  • a pictorial description of the mechanism is shown in Scheme 5, in which the catalyst center produces two polyolefin chains.
  • Scheme 5 shows how a combination of diene bridging and chain transfer may create a diene "Ladder Branched" tri-functional polymer structure.
  • diene "Ladder Branched" polymer refers to the long-chain branching, in which a short chain or rung links two polymer chains together.
  • the metal-ligand catalyst having at least two polymer chain sites propagates two separate polymer chains.
  • One alkene of the diene is incorporated into one of the sites of the catalyst, and it is believed that due to the close proximity of the propagation sites, the second alkene of the diene is then quickly incorporated into the second polymer chain, thereby forming a bridge or rung.
  • This successive addition of diene is referred to as a "concerted" addition of the diene, distinguishing it from catalysts without two proximal chains where diene addition leads to a concentration of vinyl containing polymers in the reactor, which react later.
  • rung refers to the diene once it is incorporated into two separate polymer strands, thereby linking the strands together.
  • the first and second polymer strands continue to propagate until the polymer transfers to another catalyst, the polymer is released from the catalyst, the catalyst dies, or another diene is added.
  • the polymer of this disclosure is an ethylene-based copolymer comprising at least 50 mol% ethylene.
  • ethylene-based polymer refer to homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as ⁇ -olefins, may comprise from at least 50 mole percent (mol%) monomer units derived from ethylene.
  • the ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as ⁇ -olefins may comprise at least 60 mole percent monomer units derived from ethylene; at least 70 mole percent monomer units derived from ethylene; at least 80 mole percent monomer units derived from ethylene; or from 50 to 100 mole percent monomer units derived from ethylene; or from 80 to 100 mole percent monomer units derived from ethylene.
  • a mathematical model was previously derived for tetra-functional "Ladder Branched" long-chain branching and described in Application Nos. PCTUS2019/053524 ; PCTUS2019/053527 ; PCTUS2019/053529 ; and PCTUS2019/053537, each filed September 27, 2019 .
  • a model is derived for tri-functional "Ladder Branched" long-chain branching.
  • the mathematical model will also be used to establish claims metrics and ranges.
  • the mathematical model of the branched architecture as described in this disclosure may be derived from a kinetics description of the proposed mechanism of branching. This model is based upon several assumptions to facilitate mathematical simplicity.
  • Model Derivation The first step in deriving a model of the system is to write the kinetics in symbolic form, indicating the effect of each reaction on the molecular attribute(s) of interest. It is standard practice to use indices to indicate the number of repeat units associated with a growing (living) or dead polymer chain. Furthermore, it is also recognized that addition copolymer molecular architectures can be accurately described by homopolymer kinetics and models when the homopolymer rate constants are regarded as effective composite copolymerization rate constants ( Tobita and Hamielec, Polymer 1991, 32 (14), 2641 ).
  • the kinetics are written for each of the two polymer molecules growing on the catalyst, identified as left and right.
  • the outcome of propagation is the incremental increase in a molecule size by one repeat unit, whether it be the left side (P n+1,m ) or the right side (P n,m+1 ).
  • the chain transfer reactions detach a chain from the catalyst and generate a dead polymer molecule from wither the left (D n ) or right (D m ) side. Additional simple chain transfer type reactions such as hydrogenation or beta hydride elimination do not add complexity to the model.
  • the diene bridging reaction k d is written for each catalyst side and each rate uses a factor of 2 because of the two reactive groups on a diene (D).
  • the diene bridging reaction k g uses a factor of 4 in its rate because it is written once for both (2) sides and a diene (D) has two reactive sites. Therefore, the diene consuming kinetics have rate constants which are defined on a group-wise basis rather than a molecular basis.
  • the kinetics scheme can be rendered into a series of balance equations that describe how each reaction effects the molecular architecture. In the writing of these balances it is convenient to use a shorthand nomenclature to represent each reaction rate. These rate groups are defined below.
  • R P n , m ⁇ P n ⁇ 1 , m + P n , m ⁇ 1 ⁇ 2 P n , m ⁇ 2 ⁇ + 4 ⁇ + 4 ⁇ P n , m + ⁇ m ⁇ 1 2 ⁇ V n + ⁇ L n + ⁇ n ⁇ 1 2 ⁇ V m + ⁇ R m + ⁇ n ⁇ 1 ⁇ m ⁇ 1 4 ⁇ ⁇ 0 , 0
  • R L n ⁇ L n ⁇ 1 ⁇ L n ⁇ ⁇ + 4 ⁇ + 4 ⁇ L n + 2 ⁇ V n + ⁇ n ⁇ 1 ⁇ + 2 ⁇ + 4 ⁇ ⁇ 0 , 0
  • R V n 2 ⁇ V n ⁇ 1 ⁇ V n ⁇ 2 ⁇ + 4 ⁇ + 4 ⁇ V n + 4 ⁇ V n ⁇ 1 + 2 ⁇ L n ⁇ 1 + ⁇ n ⁇ 2 4 ⁇ ⁇ 0 , 0
  • the first step in rendering a usable model is to implement the "steady-state assumption" on the growing polymer species distributions by setting the relevant polymer subspecies rates ( R Pn,m , R Ln , R Vn ) to zero.
  • R Pn,m relevant polymer subspecies rates
  • R Ln relevant polymer subspecies rates
  • R Vn relevant polymer subspecies rates
  • a model describing the moments of the polymer species chain length distributions can often be derived from population balances resulting from a kinetics scheme.
  • a moment based model is useful in predicting molecular weight averages and polydispersity index but in general does not describe smaller nuances in MWD such as bimodality, peak MW, and tailing.
  • the method of moments entails the definition of various polymeric subspecies chain length distribution moments such as those below.
  • the bulk polymer moments ( ⁇ i ) reflect bulk polymer properties and solution of a model of bulk moments generally requires solution of various living polymer moments.
  • Rates of change of the leading bulk polymer moments ( ⁇ 0 , ⁇ 1 , ⁇ 2 ) are given below with negligible terms removed after imposing the assumption that kinetic chains are long, and therefore ⁇ >> ⁇ , ⁇ » ⁇ , ⁇ >> ⁇ .
  • R ⁇ 0 2 ⁇ + 4 ⁇ ⁇ 0 , 0
  • R ⁇ 1 2 ⁇ + 8 ⁇ ⁇ 1 , 0
  • R ⁇ 2 2 ⁇ + 8 ⁇ ⁇ 2 , 0 + 8 ⁇ 1 , 1
  • the instantaneous number and weight average chain lengths (DP n , DP w ) are provided below, after evaluation algebraic simplification of the moment rates.
  • the average molecular weights (M n , M w ) are equal to the average chain lengths multiplied by the apparent monomeric repeat unit weight in g/mole.
  • the expression of the model is further simplified by a few substitutions, such as the diene-free average linear kinetic chain length DP no being equal to ⁇ / ⁇ .
  • the model can be further simplified by expressing it in terms of dimensionless instantaneous branching metrics, such as F b which is the fraction of diene junctures that are bi-functional.
  • F b dimensionless instantaneous branching metrics
  • R c is the ratio of diene junctures to original polymer molecules.
  • R c is simply a scaling for dienes junctures and is expected to increase proportionally with dienes.
  • a disadvantage of R kc is that original kinetic chain length or concentration is generally only directly available when a series of data are measured which includes a zero dienes branching level.
  • the metric R n is an alternative to the branching metric R kc , where R n is the ratio of dienes junctures to polymer molecules.
  • R n is the ratio of dienes junctures to polymer molecules.
  • the use of R n to analyze data is facilitated by the measurability of chain length or concentration through GPC measurement of number average molecular weight.
  • FIG. 2 demonstrates the effects of dienes juncture functionality (F b ) on the molecular weight and polydispersity of polymers.
  • the model clearly shows that pure tri-functional dienes bridging has a limited twofold potential effect on molecular weight and polydispersity and that the incremental effect diminishes at high dienes levels such as R kc >3.
  • a modest bi-functional dienes juncture level of F b 5% or 10% is expected then it is possible that experimental data might not even prove a positive correlation between dienes level and M w .
  • Alternate assignments for the X(n) function terms can be rendered using the branching metrics (F b , R kc , R n ) applied earlier to the instantaneous average chain length and molecular weight model.
  • Integrals of X(n) can be used to express number and weight average chain lengths as well as polydispersity.
  • DP n ⁇ 0 ⁇ n X n dn
  • DP w ⁇ 0 ⁇ n 2 X n dn / ⁇ 0 ⁇ n X n dn
  • ⁇ 0 ⁇ X n dn 1
  • FIG. 3 is a series of simulated SEC curves wherein the level of tri-functional branching (B c or B n ) is varied.
  • the independent variable in FIG. 3 is scaled by linear molecular weight or chain length such that the plotting is universal and independent of starting molecular weight.
  • the zero-branching case in FIG. 3 is the well-known "most probable" MWD and is expected for linear addition co-polymerization performed under ideal homogeneous conditions.
  • FIG. 4 is a plot of relative peak MW for tri-functional dienes branching which demonstrates that the MWD peak is most sensitive to branching level at intermediate branching levels in the approximate range of 0.2 ⁇ B n ⁇ 0.9 or 0.17 ⁇ B c ⁇ 0.5.
  • the purpose of this section is to compare a variety of conventional dienes branching and random polymer coupling to the "Ladder Branching" models.
  • the comparison demonstrates the inherent instability of conventional dienes branching and random polymer coupling in contrast to "Ladder Branching".
  • the molecular architecture resulting from the dienes "Ladder Branching” is different from (a) the conventional Dienes Continuous Stirred Tank Reactor (CSTR) Branching Model, (b) conventional Dienes Semi-Batch Branching Model; (c) Polymer CSTR Coupling Model; and (d) Polymer Batch Coupling Model.
  • a high level of natural LCB in a polymer is difficult to achieve due to the limited concentration of vinyl terminated polymers (maximum one per polymer chain) and the need to run to high conversion to ensure LCB formation. To ensure high conversion, there is a low ethylene concentration in the reactor, thus enabling a great amount of vinyl terminated polymers to be reinserted in a second polymer chain.
  • Carbons on the silicon of the tetra-functional branched polymer are shifted upfield relative to the carbons on the silicon of the tri-functional branched polymer (see FIG. 8 ). Examples will show that control of the tri-functional to tetra-functional long-chain branch ratio is possible.
  • the conventional process of incorporating dienes into a polymer synthesis system suffers from the fundamental flaw of gel formation or reactor fouling at high branching levels.
  • the kinetic modeling discussed in previous paragraphs, may provide good predictive results that enable a better understanding of gel formation. For example, longer polymer chains have proportionally more pendant vinyls and polymer chains containing more pendant vinyls will more likely re-insert into the catalyst to form a LCB.
  • the larger polymer chains preferentially re-insert forming tetra-functional branches, which are even larger polymer molecules, and a gel problem or instability results when the LCB level reaches a threshold value.
  • FIG. 1 A simulation of the weight average molecular weight (M w ) and number average molecular weight (M n ) as a function of conventional tetra-functional branching is shown in FIG. 1 for ethylene-based polymer in a semi-batch reactor at constant pressure.
  • M n only marginally increases as M w becomes infinite.
  • MWD polymer molecular weight distribution
  • the MWD is defined by the weight average molecular weight, M w , divided by the number average molecular weight, M n , (M w /M n ).
  • Polymer gels are narrowly defined for the purpose of this disclosure to be a polymer fraction that is phase separated due to its high branching level and/or high molecular weight. Polymer gels can be observed in solution or in the melt and tend to interfere with properties such as optical clarity and film and fiber performance. Polyethylene interpolymer gels can be measured by degree of polymer insolubility in hot xylene. Gels content is often correlated to and therefore estimated from GPC polymer recovery percentage. When polymer gels form, they may deposit within the reactor and result in fouling.
  • high MW tailing or “high molecular weight tail” refers to the high molecular weight fraction as shown by the conventional GPC and the absolute GPC. Depending on catalyst-diene pairing and experimental conditions, one might expect a "Ladder Branched” system to have some conventional branching thereby raising the shape metric value above that expected for pure "Ladder Branching".
  • a HIGH or A TAIL increase dramatically as the conventional branching level is increased.
  • the "Ladder Branching" model (tetra-functional or tri-functional) predicts that the high MW area metrics (A HIGH or A TAIL ) are almost unaffected by "Ladder Branching" level.
  • the values of A HIGH and A TAIL for a most probable MWD are about 0.07 and 0.015, respectively.
  • Example MWD data will demonstrate that the dienes-free linear polymers tend to have slightly higher values of A HIGH and A TAIL due to non-ideal aspects of the polymerization.
  • Example data also show a variety of highly branched "Ladder Branched" polymers with essentially no high MW tail beyond what is expected from a most probable MWD.
  • the high MW area metrics also are diagnostic of slight levels of high MW tail formation that "Ladder Branched" polymer can exhibit when accompanied by a degree of conventional branching.
  • the metric A TAIL is less influenced by linear MWD non-ideality than A HIGH .
  • a HIGH and A TAIL metrics are equally indicative of high MW tail formation.
  • the polymers of this disclosure have tri-functional long-chain branching levels of greater than 0.1 per 1000 carbon atoms. In some embodiments, the polymers of this disclosure have tri-functional long-chain branching levels of greater than 0.2 per 1000 carbon atoms, greater than 0.3 per 1000 carbon atoms, greater than 0.4 per 1000 carbon atoms, or greater than 0.5 per 1000 carbon atoms.
  • the ethylene-based polymers of this disclosure include a melt viscosity ratio or rheology ratio (V 0.1 /V 100 ) at 190 °C of at least 10, where V 0.1 is the viscosity of the ethylene-based polymer at 190 °C at an angular frequency of 0.1 radians/second, and V 100 is the viscosity of the ethylene-based polymer at 190 °C at an angular frequency of 100 radians/second.
  • the melt viscosity ratio is at least 14, at least 20, at least 25, or at least 30.
  • the melt viscosity ratio is greater than 50, at least 60, or greater than 100.
  • the melt viscosity ratio is from 14 to 200.
  • the "rheology ratio” and “melt viscosity ratio” are defined by V 0.1 /V 100 at 190 °C, where V 0.1 is the viscosity of the ethylene-based polymer at 190 °C at an angular frequency of 0.1 radians/second, and V 100 is the viscosity of the ethylene-based polymer at 190 °C at an angular frequency of 100 radians/second.
  • the ethylene-based polymers of this disclosure have an average g' less than 0.86, where the average g' is an intrinsic viscosity ratio determined by gel permeation chromatography using a triple detector. In some embodiments, the ethylene-based polymers of this disclosure have an average g' from 0.55 to 0.86. All individual values and subranges encompassed by "from 0.55 to 0.86" are disclosed herein as separate embodiments; for example, the average g' of the ethylene-based polymer may range from 0.64 to 0.75, from 0.58 to 0.79, or from 0.65 to 0.83. In one or more embodiments, the average g' is from 0.55 to 0.84, from 0.59 to 0.82, or from 0.66 to 0.80.
  • the melt viscosity ratio of the ethylene-based polymer of this disclosure may be greater than ten times the elasticity factor where the melt viscosity ratio (V 0.1 /V 100 ) is determined by V 0.1 , the viscosity of the ethylene-based polymer at 190 °C at an angular frequency of 0.1 radians/second, and V 100 , the viscosity of the ethylene-based polymer at 190 °C at an angular frequency of 100 radians/second, and the elasticity factor m is [((tan ( ⁇ 0.1 ) - tan ( ⁇ 100 ))*1000)/(0.1-100))], wherein tan ( ⁇ 0.1 ) is the tangent of the phase angle at 0.1 radians/second, and tan ( ⁇ 100 ) is the tangent of the phase angle at 100 radians/second.
  • the ethylene-based polymer may have an elasticity factor m at 190°C that is less than or equal to 8 seconds/radian, where m is [((tan ( ⁇ 0.1 ) - tan ( ⁇ 100 ))*1000)/(0.1-100))]. In other embodiments, the ethylene-based polymer may have an elasticity factor m at 190°C that is less than or equal to 4 seconds/radian.
  • the melt strength of the ethylene-based polymer of this disclosure may be greater than 6 cN (Rheotens device, 190°C, 2.4 mm/s 2 , 120 mm from the die exit to the center of the wheels, extrusion rate of 38.2 s -1 , capillary die of 30 mm length, 2 mm diameter and 180° entrance angle). In some embodiments, the melt strength of the ethylene-based polymer may be greater than 10 cN.
  • the ethylene-based polymer may have a molecular weight tail quantified by an MWD area metric A TAIL , and A TAIL is less than or equal to 0.04. All individual values and subranges encompassed by "less than or equal to 0.04" are disclosed herein as separate embodiments.
  • the A TAIL of the ethylene-based polymer of this disclosure is greater than 0 and less than or equal to 0.03 as determined by gel permeation chromatography using a triple detector.
  • the polymer of this disclosure may have a weight average molecular weight (M w ) of less than or equal to 800,000 Daltons, as determined by gel permeation chromatography using a triple detector. In various embodiments, the polymer may have a weight average molecular weight (M w ) of less than or equal to 400,000 Daltons, less than or equal to 200,000 Daltons, or less than or equal to 150,000 Daltons, as determined by gel permeation chromatography using a triple detector.
  • the polymer of this disclosure may have an M w /M n (weight average molecular weight / number average molecular weight) of less than or equal to 6, as determined by gel permeation chromatography using a triple detector. In various embodiments, the polymer may have a have an M w /M n of less than 5, or less than 4 as determined by gel permeation chromatography using a triple detector. In some embodiments, the MWD of the long chain branches polymer is from 1 to 3; and other embodiments include MWD from 1.5 to 2.5.
  • Each M w0 and the M p0 is a metric of polymer resins without the addition of diene into the reactor during polymerization, as previously discussed. Each subsequent addition of diene produces a polymer resin from which the metric M w or M p may be determined.
  • the amount of diene incorporated into the reactor is small in comparison to the other reactants in the reactor. Therefore, the addition of diene does not affect the total amount of comonomer, ethylene, and solvent in the reactor.
  • the ethylene-based polymer has a gpcBR branching index of from 0.1 to 3.0. All individual values and subranges encompassed by "from 0.10 to 3.00" are disclosed herein as separate embodiments; for example, the ethylene-based polymers, may include a gpcBR branching index of from 0.10 to 2.00, from 0.10 to 1.00, from 0.15 to 0.65, from 0.20 to 0.75, or 0.10 to 0.95.
  • the long-chain branching polymerization processes described in the preceding paragraphs are utilized in the polymerization of olefins, primarily ethylene and propylene.
  • olefins primarily ethylene and propylene.
  • additional ⁇ -olefins may be incorporated into the polymerization procedure.
  • the additional ⁇ -olefin co-monomers typically have no more than 20 carbon atoms.
  • the ⁇ -olefin co-monomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms.
  • Exemplary ⁇ -olefin co-monomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, and ethylidene norbornene.
  • the one or more ⁇ -olefin co-monomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1-hexene and 1-octene.
  • the long-chain branched polymer for example homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as ⁇ -olefins, may comprise at least 50 percent by weight of units derived from ethylene.
  • ethylene-based polymers, homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more co-monomers such as ⁇ -olefins may compri se at least 60 percent by weight of units derived from ethylene; at least 70 percent by weight of units derived from ethylene; at least 80 percent by weight of units derived from ethylene; or from 50 to 100 percent by weight of units derived from ethylene; or from 80 to 100 percent by weight of units derived from ethylene.
  • the ethylene-based polymer includes additional ⁇ -olefin.
  • the amount of additional ⁇ -olefin in the ethylene-based polymer is less than or equal to 50 mole percent (mol%); other embodiments the amount of additional ⁇ -olefin includes at least 0.01 mol% to 25 mol%; and in further embodiments the amount of additional ⁇ -olefin includes at least 0.1 mol% to 10 mol%.
  • the additional ⁇ -olefin is 1-octene.
  • the long-chain branched polymers may comprise at least 50 percent by moles of units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments.
  • the ethylene based polymers may comprise at least 93 percent by moles of units derived from ethylene; at least 96 percent by moles of units; at least 97 percent by moles of units derived from ethylene; or in the alternative, from 90 to 100 percent by moles of units derived from ethylene; from 90 to 99.5 percent by moles of units derived from ethylene; or from 97 to 99.5 percent by moles of units derived from ethylene.
  • the amount of additional ⁇ -olefin is less than 50%; other embodiments include at least 1 mole percent (mol%) to 20 mol%; and in further embodiments the amount of additional ⁇ -olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional ⁇ -olefin is 1-octene.
  • Any conventional polymerization processes may be employed to produce the long-chain branched polymer.
  • Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel, series, or any combinations thereof, for example.
  • the ethylene based polymer may be produced via solution polymerization in a dual reactor system, for example a single loop reactor system, wherein ethylene and optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system, as described herein, and optionally one or more co-catalysts.
  • the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system in this disclosure, and as described herein, and optionally one or more other catalysts.
  • the catalyst system can be used in the first reactor, or second reactor, optionally in combination with one or more other catalysts.
  • the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene and optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system, as described herein, in both reactors.
  • the long-chain branched polymer may be produced via solution polymerization in a single reactor system, for example a single loop reactor system, in which ethylene and optionally one or more ⁇ -olefins are polymerized in the presence of the catalyst system, as described within this disclosure, and optionally one or more co-catalysts, as described in the preceding paragraphs.
  • the long-chain branching polymerization process for producing the long-chain branched polymer includes polymerizing ethylene and at least one additional ⁇ -olefin in the presence of a catalyst system.
  • the long-chain branched polymers may further comprise one or more additives.
  • additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof.
  • the ethylene-based polymers may contain any amounts of additives.
  • the ethylene-based polymers may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the ethylene based polymers and the one or more additives.
  • the ethylene-based polymers may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers.
  • the long-chain branched polymers may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH) 2 , based on the combined weight of the ethylene based polymers and all additives or fillers.
  • the ethylene-based polymers may further be blended with one or more polymers to form a blend.
  • the long-chain polymerization process for producing long-chain branched polymers may include polymerizing ethylene and at least one additional ⁇ -olefin in the presence of a catalyst having two polymer producing sites.
  • the long-chain branched polymer resulting from such the catalyst having two polymer producing sites may have a density according to ASTM D792 from 0.850 g/cm 3 to 0.960 g/cm 3 , from 0.880 g/cm 3 to 0.920 g/cm 3 , from 0.880 g/cm 3 to 0.910 g/cm 3 , or from 0.880 g/cm 3 to 0.900 g/cm 3 , for example.
  • the long-chain branched polymer resulting from the long-chain polymerization process may have a melt flow ratio (I 10 /I 2 ) from 5 to 100, in which melt index I 2 is measured according to ASTM D1238 at 190 °C and 2.16 kg load, and melt index I 10 is measured according to ASTM D1238 at 190 °C and 10 kg load.
  • melt flow ratio (I 10 /I 2 ) is from 5 to 50, in others, the melt flow ratio is from 5 to 25, in others, the melt flow ratio is from 5 to 9.
  • the chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) and 4-capillary viscometer (DV) coupled to a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. For all absolute Light scattering measurements, the 15 degree angle is used for measurement.
  • the autosampler oven compartment was set at 160° Celsius and the column compartment was set at 150° Celsius.
  • the columns used were 4 Agilent "Mixed A" 30cm 20-micron linear mixed-bed columns.
  • the chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT).
  • BHT butylated hydroxytoluene
  • the solvent source was nitrogen sparged.
  • the injection volume used was 200 microliters and the flow rate was 1.0 milliliters/minute.
  • Calibration of the GPC column set was performed with at least 20 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and were arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights.
  • the standards were purchased from Agilent Technologies.
  • the polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000.
  • the polystyrene standards were dissolved at 80 degrees Celsius with gentle agitation for 30 minutes.
  • a polynomial between 3 rd and 5 th order was used to fit the respective polyethylene-equivalent calibration points.
  • a small adjustment to A was made to correct for column resolution and band-broadening effects such that NIST standard NBS 1475 is obtained at 52,000Mw.
  • the total plate count of the GPC column set was performed with Eicosane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle agitation).
  • Symmetry Rear Peak RV one tenth height ⁇ RV Peak Max RV Peak Max ⁇ Front Peak RV one tenth height
  • RV is the retention volume in milliliters and the peak width is in milliliters
  • Peak max is the maximum position of the peak
  • one tenth height is 1/10 height of the peak maximum
  • rear peak refers to the peak tail at later retention volumes than the peak max
  • front peak refers to the peak front at earlier retention volumes than the peak max.
  • the plate count for the chromatographic system should be greater than 24,000 and symmetry should be between 0.98 and 1.22.
  • Samples were prepared in a semi-automatic manner with the PolymerChar "Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 2 hours at 160° Celsius under "low speed” shaking.
  • M n(GPC) , M w(GPC) , and M z(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 51-53, using PolymerChar GPCOne TM software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1.
  • a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system.
  • This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run.
  • a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position.
  • the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation 7. Processing of the flow marker peak was done via the PolymerChar GPCOne TM Software. Acceptable flowrate correction is such that the effective flowrate should be within +/-2% of the nominal flowrate.
  • Flowrate effective Flowrate nominal * RV FM Calibrated / RV FM Sample
  • TGPC Triple Detector GPC
  • the Systematic Approach for the determination of multi-detector offsets is done in a manner consistent with that published by Balke, Mourey, et. al. ( Mourey and Balke, Chromatography Polym. Chpt 12, (1992 )) ( Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992 )), optimizing triple detector log (MW and IV) results from a broad homopolymer polyethylene standard (M w /M n > 3) to the narrow standard column calibration results from the narrow standards calibration curve using PolymerChar GPCOne TM Software.
  • the absolute molecular weight data is obtained in a manner consistent with that published by Zimm ( Zimm, B.H., J. Chem. Phys., 16, 1099 (1948 )) and Kratochvil ( Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987 )) using PolymerChar GPCOne TM software.
  • the overall injected concentration, used in the determination of the molecular weight, is obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known weight average molecular weight.
  • the calculated molecular weights are obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn/dc, of 0.104.
  • the mass detector response (IR5) and the light scattering constant (determined using GPCOne TM ) may be determined from a linear standard with a molecular weight in excess of about 50,000 g/mole.
  • the viscometer calibration (determined using GPCOne TM ) may be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)).
  • SRM Standard Reference Materials
  • a viscometer constant (obtained using GPCOne TM ) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity.
  • the chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight).
  • the absolute weight average molecular weight (M w(Abs) ) is obtained (using GPCOne TM )from the Area of the Light Scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area.
  • the molecular weight and intrinsic viscosity responses are linearly extrapolated at chromatographic ends where signal to noise becomes low (using GPCOne TM ).
  • the complex viscosity ( ⁇ *), moduli (G', G"), tan delta, and phase angle ( ⁇ ) are obtained by dynamic oscillatory frequency sweep test in a frequency range from 0.1 to 100 rad/s, at 190 °C.
  • the level of strain is set within the linear viscoelastic regime as identify by a strain sweep test at 100 rad/s at 190 °C.
  • Tests are performed with stainless steel parallel plates of 25 mm diameter on a strain controlled rheometer ARES-G2 by TA Instruments. Samples of 3.3 mm thickness are squeezed and then trimmed in two steps prior to the actual test. In the first step, the sample are allowed to melt for 2.5 min, squeezed to 3 mm gap and trimmed. After an additional 2.5 min of soak time at 190 °C, the sample are squeezed to 2 mm gap, and the excess of material trimmed. The method has an additional five minute delay built in to allow the system to reach thermal equilibrium. Tests are performed under nitrogen atmosphere.
  • TDGPC Triple Detector GPC
  • the gpcBR branching index was determined by first calibrating the light scattering, viscosity, and concentration detectors as described previously. Baselines were then subtracted from the light scattering, viscometer, and concentration chromatograms. Integration windows were then set, to ensure integration of all of the low molecular weight retention volume range in the light scattering and viscometer chromatograms that indicate the presence of detectable polymer from the refractive index chromatogram. Linear polyethylene standards were then used to establish polyethylene and polystyrene Mark-Houwink constants.
  • the gpcBR branching index is a robust method for the characterization of long chain branching as described in Yau, Wallace W., "Examples of Using 3D-GPC - TREF for Poly-olefin Characterization," Macromol. Symp., 2007, 257, 29-45 .
  • the index avoids the "slice-by-slice" TDGPC calculations traditionally used in the determination of g' values and branching frequency calculations, in favor of whole polymer detector areas. From TDGPC data, one can obtain the sample bulk absolute weight average molecular weight (M w , abs) by the light scattering (LS) detector, using the peak area method.
  • the method avoids the "slice-by-slice" ratio of light scattering detector signal over the concentration detector signal, as required in a traditional g' determination.
  • sample intrinsic viscosities were also obtained independently using Equation (63).
  • the area calculation in this case offers more precision, because, as an overall sample area, it is much less sensitive to variation caused by detector noise and TDGPC settings on baseline and integration limits. More importantly, the peak area calculation was not affected by the detector volume offsets.
  • DPi stands for the differential pressure signal monitored directly from the online viscometer.
  • the light scattering elution area for the sample polymer was used to determine the molecular weight of the sample.
  • the viscosity detector elution area for the sample polymer was used to determine the intrinsic viscosity (IV or [ ⁇ ]) of the sample.
  • the weight average molecular weight by light scattering is commonly referred to as “absolute weight average molecular weight” or “M w (abs).”
  • M w,cc from using conventional GPC molecular weight calibration curve is often referred to as "polymer chain backbone molecular weight,” “conventional weight average molecular weight” and “M w (conv).”
  • gpcBR The interpretation of gpcBR is straight forward. For linear polymers, gpcBR will be close to zero, since the values measured by LS and viscometry will be close to the conventional calibration standard. For branched polymers, gpcBR will be higher than zero, especially with high levels of long chain branching, because the measured polymer molecular weight will be higher than the calculated M w,cc , and the calculated IV cc will be higher than the measured polymer IV. In fact, the gpcBR value represents the fractional IV change due to the molecular size contraction effect as a result of polymer branching.
  • a gpcBR value of 0.5 or 2.0 would mean a molecular size contraction effect of IV at the level of 50% and 200%, respectively, versus a linear polymer molecule of equivalent weight.
  • the advantage of using gpcBR, in comparison to a traditional "g' index" and branching frequency calculations, is due to the higher precision of gpcBR. All of the parameters used in the gpcBR index determination are obtained with good precision, and are not detrimentally affected by the low TDGPC detector response at high molecular weight from the concentration detector. Errors in detector volume alignment also do not affect the precision of the gpcBR index determination.
  • the raw polymer samples contained solvent and catalyst residues which must be removed prior to NMR measurements of unsaturation and branching.
  • the polymers were first dissolved in tetrachloroethane (TCE) at 120-125 °C, then precipitated using 3-Propanol (IPA) and cooled to room temperature. The polymer was isolated by centrifugation. This process of washing the polymer was repeated at least 3 times. The resulting polymer was then dried in a vacuum oven at 50 °C.
  • TCE tetrachloroethane
  • IPA 3-Propanol
  • the batch reactor polymerization reactions are conducted in a 2 L Parr TM batch reactor.
  • the reactor is heated by an electrical heating mantle, and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating/cooling system are controlled and monitored by a Camile TM TG process computer.
  • the bottom of the reactor is fitted with a dump valve that empties the reactor contents into a stainless steel dump pot.
  • the dump pot is prefilled with a catalyst kill solution (typically 5 mL of an Irgafos / Irganox / toluene mixture).
  • the dump pot is vented to a 30 gallon blow-down tank, with both the pot and the tank purged with nitrogen.
  • All solvents used for polymerization or catalyst makeup are run through solvent purification columns to remove any impurities that may affect polymerization.
  • the 1-octene and IsoparE are passed through two columns, the first containing A2 alumina, the second containing Q5.
  • the ethylene is passed through two columns, the first containing A204 alumina and 4 ⁇ molecular sieves, the second containing Q5 reactant.
  • the N 2 used for transfers, is passed through a single column containing A204 alumina, 4 ⁇ molecular sieves and Q5.
  • the reactor is loaded first from the shot tank that may contain IsoparE solvent and/or 1-octene, depending on reactor load.
  • the shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted.
  • the reactor is heated up to the polymerization temperature set point. If ethylene is used, it is added to the reactor when the ethylene is at the reaction temperature to maintain reaction pressure set point. The amount of ethylene added is monitored by a micro-motion flow meter (Micro Motion).
  • the standard conditions at 150 °C are 13 g ethylene, 15 g 1-octene, 240 psi hydrogen in 585 g of IsoparE, and the standard conditions at 150 °C are 15 g ethylene, 45 g 1-octene, 200 psi hydrogen in 555 g of IsoparE.
  • the procatalyst and activators are mixed with the appropriate amount of purified toluene to achieve a desired molarity solution.
  • the procatalyst and activators are handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. The syringe is rinsed three times with 5 mL of toluene.
  • the run timer begins. If ethylene is used, it is added by the Camile to maintain reaction pressure set point in the reactor. The polymerization reactions are run for 10 minutes, then the agitator is stopped, and the bottom dump valve is opened to empty reactor contents to the dump pot.
  • the contents of the dump pot are poured into trays and placed in a lab hood where the solvent was evaporated off overnight.
  • the trays containing the remaining polymer are transferred to a vacuum oven, where they are heated up to 140 °C under vacuum to remove any remaining solvent. After the trays cool to ambient temperature, the polymers were weighed for yield to measure efficiencies, and submitted for polymer testing.
  • Table 2 collects data for the comparative example, 1.C and other diene examples, 1.1-1.7. NMR data demonstrate both tri-functional and tetra-functional LCB and increasing levels of LCB with increasing diene.
  • FIG. 6 depicts the conventional molecular weight distributions for the examples with different amounts of diene.
  • Table 3 collects data for the comparative example, 2.C and diene example, 2.1. NMR data demonstrate both tri-functional (0.15 LCB/1000C) and tetra-functional (0.10 LCB/1000C) in a ratio of 1.4:1 (tri:tetra LCB).
  • the Dynamic Mechanical Spectrum of the branched Example 2.1 was measured and the results recorded in Table 3.
  • the viscosity at 0.1 radians/second was determined to be 609,361 Pa s and the viscosity at 100 radians/second was measured to be 2,453 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 248.4.
  • Table 4 collects data for the comparative example, 3.C and diene example, 1.1. NMR data demonstrate both tri-functional (0.23 LCB/1000C) and tetra-functional (0.13 LCB/1000C) in a ratio of 1.8:1 (tri:tetra LCB).
  • the Dynamic Mechanical Spectrum of the branched Example 3.1 was measured and the results recorded in Table 4.
  • the viscosity at 0.1 radians/second was determined to be 515,022 Pa s and the viscosity at 100 radians/second was measured to be 2,140 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 240.6.
  • Table 5 collects data for the comparative example, 4.C and diene example, 4.1. NMR data demonstrate both tri-functional (0.31 LCB/1000C) and tetra-functional (0.30 LCB/1000C) in a ratio of 1.03:1 (tri:tetra LCB).
  • the Dynamic Mechanical Spectrum of the branched Example 4.1 was measured and the results recorded in Table 5.
  • the viscosity at 0.1 radians/second was determined to be 867,379 Pa s and the viscosity at 100 radians/second was measured to be 2,818 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 307.8.
  • Table 6 collects data for the comparative example, 5.C and diene example, 5.1. NMR data demonstrate both tri-functional (0.25 LCB/1000C) and tetra-functional (0.30 LCB/1000C) in a ratio of 0.8:1 (tri:tetra LCB).
  • the Dynamic Mechanical Spectrum of the branched Example 5.1 was measured and the results recorded in Table 6.
  • the viscosity at 0.1 radians/second was determined to be 813,746 Pa s and the viscosity at 100 radians/second was measured to be 2,742 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 296.7.
  • Table 7 collects data for diene examples, 6.1, 6.2, and 6.3.
  • Examples 6.2 and 6.3 indicate different catalysts can form different amount of tri-functional LCB and different ratios of tri-functional LCB: tetra-functional LCB.
  • Catalyst 1 Example 6.2
  • Catalyst 2 Example 6.3
  • the amount tri-functional LCB and the ratio of tri-functional:tetra-functional LCB depends very much on the catalyst.
  • Examples 6.1 and 6.2 indicate polymerizations runs under comparable conditions with the key difference being that Example 6.1 contains octene while Example 6.2 does not contain octene.
  • the amount of tri-functional LCB and the ratio of tri-functional:tetra-functional LCB is very similar in the two runs.
  • the Dynamic Mechanical Spectrum of the Example 6.1 was measured and the results recorded in Table 7.
  • the viscosity at 0.1 radians/second was determined to be 306,441 Pa s and the viscosity at 100 radians/second was measured to be 1,754 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 174.7.
  • Table 8 Polymer runs and characteristics of the batch reactor polymer of Example 7 and the comparative. Ex. Diene Added (g) Yield (g) Octene (mol%) T m (°C) Conventional GPC Data and Metrics NMR per 1000C Mn Mw Mp A TAIL Tetra-functio nal LCB Tri-functio nal LCB (g/mole) 7.C 0.0 4.8 7.0 83.9 22,315 54,685 47,863 0.030 0.00 0.00 7.1 0.4 2.5 4.6 98.1 31,836 158,106 109,648 0.022 0.14 0.00 Table 8: Continued Absolute GPC Data and Metrics Ex.
  • Table 8 collects data for the comparative example, 7.C and diene example, 7.1. NMR data demonstrated no tri-functional in this example with no hydrogen present. Tetra-functional LCB exists (0.14 LCB/1000C) and the ratio of tri-functional:tetra-functional is zero.
  • Example 7.1 The Dynamic Mechanical Spectrum of Example 7.1 was measured and the results recorded in Table 8.
  • the viscosity at 0.1 radians/second was determined to be 475,848 Pa s and the viscosity at 100 radians/second was measured to be 1,982 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 240.1.
  • Table 9 collects data for the comparative example, 8.C and diene example, 8.1. NMR data demonstrate both tri-functional (0.09 LCB/1000C) and tetra-functional (0.11 LCB/1000C) in a ratio of 0.8:1 (tri:tetra LCB).
  • Example 8.1 The Dynamic Mechanical Spectrum of Example 8.1 was measured and the results recorded in Table 9. The viscosity at 0.1 radians/second was determined to be 721,022 Pa s and the viscosity at 100 radians/second was measured to be 2,297 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 313.8.
  • Table 10 collects data for the comparative example, 9.C and diene example, 9.1. NMR data demonstrate both tri-functional (0.09 LCB/1000C) and tetra-functional (0.10 LCB/1000C) in a ratio of 0.9:1 (tri:tetra LCB).
  • Example 9.1 The Dynamic Mechanical Spectrum of Example 9.1 was measured and the results recorded in Table 10.
  • the viscosity at 0.1 radians/second was determined to be 697,565 Pa s and the viscosity at 100 radians/second was measured to be 2,782 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 250.7.
  • Table 11 collects data for the comparative example, 10.C and diene example, 10.1. NMR data demonstrate both tri-functional (0.07 LCB/1000C) and tetra-functional (0.10 LCB/1000C) in a ratio of 0.7:1 (tri:tetra LCB).
  • Example 10.1 The Dynamic Mechanical Spectrum of Example 10.1 was measured and the results recorded in Table 11.
  • the viscosity at 0.1 radians/second was determined to be 240,894 Pa s and the viscosity at 100 radians/second was measured to be 1,642 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 146.7.
  • Table 12 collects data for the comparative example, 11.C and diene example, 11.1. NMR data demonstrate both tri-functional (0.09 LCB/1000C) and tetra-functional (0.06 LCB/1000C) in a ratio of 1.5:1 (tri:tetra LCB).
  • Example 11.1 The Dynamic Mechanical Spectrum of the Example 11.1 was measured and the results recorded in Table 12.
  • the viscosity at 0.1 radians/second was determined to be 203,979 Pa s and the viscosity at 100 radians/second was measured to be 1,523 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 133.9.
  • the measured melt-strength of the polymer of Example 11.1 was 18 cN with an extensibility of 32 mm/s.
  • Table 13 collects data for the comparative example, 12.C and diene example, 12.1. NMR data demonstrate both tri-functional (0.08 LCB/1000C) and tetra-functional (0.06 LCB/1000C) in a ratio of 1.3:1 (tri:tetra LCB) (see FIG. 7 - FIG. 9 ).
  • the extensional viscosity fixture (EVF) for Example 12.1 is shown in FIG. 11 .
  • the measured melt-strength of the polymer of Example 12.1 was 19 cN with an extensibility of 32 mm/s (see FIG. 12 ).
  • the Dynamic Mechanical Spectrum of the Example 12.1 was measured and the results recorded in Table 13.
  • the viscosity at 0.1 radians/second was determined to be 395,948 Pa s and the viscosity at 100 radians/second was measured to be 2,075 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 190.8 (see FIG. 13 ).
  • Table 14 collects data for the comparative example, 13.C and diene example, 13.1. NMR data demonstrate both tri-functional (0.12 LCB/1000C) and tetra-functional (0.07 LCB/1000C) in a ratio of 1.7:1 (tri:tetra LCB).
  • Example 13.1 The Dynamic Mechanical Spectrum of the Example 13.1 was measured and the results recorded in Table 14.
  • the viscosity at 0.1 radians/second was determined to be 53,390 Pa s and the viscosity at 100 radians/second was measured to be 887 Pa s, providing a rheology ratio (V 0.1 /V 100 ) of 60.2.
  • the measured melt-strength of the polymer of Example 13.1 was 10 cN with an extensibility of 65 mm/s.
  • Example 7 (Table 8) to Example 13 (Table 14) indicate that for a given catalyst and comparable conditions, control of the ratio of tri-functional to tetra-functional LCB can be controlled by the ratio of hydrogen to ethylene in the reactor, supporting the mechanism in Scheme 6.
  • Example 7 (Table 8) to Example 13 (Table 14) indicate that as the ratio of tri-functional to tetra-functional LCB is increased, M w /M w0 is systematically decreased where M w is the weight averaged molecular weight of the diene branched sample and M w0 is the weight averaged molecular weight of the unbranched comparative sample.
  • the reduced increase in M w as a higher ratio of tri-functional branching is included supports the tri-functional kinetic model here and the previously derived tetra-functional model as described in US Provisional Applications 62/738,606 , 62/73,8612 , 62/738,621 , and 62/738,633, each application filed on September 28, 2018 .
  • Guzman-2010's data were gathered at steady state while operating a CSTR at a pressure of 525 psig and a temperature of 155 °C over a range of diene feed concentrations.
  • the various steady-state polymer samples collected by Guzman-2010 contained no measurable levels of gels or insoluble material. However, at the highest level of dienes feed some minor internal reactor fouling was observed, and it was anticipated that higher levels of dienes feed would result in gels formation or reactor MWD instability.
  • the data in Guzman-2010 demonstrated how changes in conventional diene branching level affects average molecular weight and polydispersity as well as properties such as viscosity, as reflected by I 2 and I 10 .
  • the effect of conventional diene branching on molecular weight was shown for both absolute and conventional MWD measurement techniques. While absolute MWD measurement is the preferred method for branched polymers, it is not always available. Therefore, Guzman-2010 also contains molecular weights measured by conventional techniques using a refractive index detector.
  • the results in Table 33 demonstrated that, by either measurement technique, the weight average molecular weight (M w ) rises substantially as the diene feed is increased from zero to 923 ppm.
  • the molecular weight distributional data in FIG. 14A and FIG. 14B were reduced to simple metrics describing the evolution of the MWD curve position and shape as more diene monomers were fed to the CSTR.
  • the data showed these MWD metrics for both absolute and conventional MWD measurements of the Guzman-2010's polymer samples.
  • Absolute MWD measurement data showed up to an 87% increase in molecular weight as 1,9-decadiene feed ranged from 0 to 923 ppm.
  • Peak molecular weight change, as indicated by M p does not vary significantly for either means of molecular weight measurement, which is inconsistent with "Ladder branched" polymer results.
  • the shape factors are summarized in Table 34 (Guzman-2010) and are inconsistent with "Ladder branched” polymers because the values for both G 79/29 and A TAIL increased as the diene feed level and M w increased.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (16)

  1. Polymère comprenant le produit polymérisé de l'éthylène, au moins un comonomère diénique, et facultativement au moins un comonomère en C3 à C14, dans lequel :
    le diène a une structure selon la formule (I) :
    Figure imgb0086
    où X est SiR2 ou GeR2, dans lequel chaque R est indépendamment hydrocarbyle en C1-C12 ou -H ; et
    le polymère comprend des ramifications trifonctionnelles à longue chaîne résultant du diène qui se produisent à une fréquence d'au moins 0,03 pour 1 000 atomes de carbone du polymère, tel que déterminé par RMN.
  2. Polymère selon la revendication 1, dans lequel X dans la formule (I) est - Si(R)2-, et dans lequel chaque R est alkyle en C1-C12.
  3. Polymère selon la revendication 2, dans lequel le diène est le diméthyldivinylsilane.
  4. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère est un copolymère à base d'éthylène comprenant au moins 50 % en moles d'éthylène.
  5. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère est défini par une queue de masse moléculaire, qui est quantifiée par une métrique de surface de distribution de masses moléculaire (MWD), AQUEUE, dans lequel AQUEUE est inférieure ou égale à 0,04, telle que déterminée par chromatographie par perméation de gel à l'aide d'un triple détecteur.
  6. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a un g' moyen allant de 0,55 à 0,86, où le g' moyen est un rapport de viscosité intrinsèque déterminé par chromatographie par perméation de gel à l'aide d'un triple détecteur.
  7. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a un rapport de viscosité à l'état fondu (V0,1/V100) à 190 °C d'au moins 20, où V0,1 est la viscosité du polymère à 190 °C à un taux de cisaillement de 0,1 radian/seconde, et V100 est la viscosité du polymère à base d'éthylène
    à 190 °C à un taux de cisaillement de 100 radians/seconde, tel que déterminé par spectre mécanique dynamique.
  8. Polymère selon la revendication 7, dans lequel le rapport de viscosité à l'état fondu (V0,1/V100) à 190 °C est d'au moins 50, tel que déterminé par spectre mécanique dynamique.
  9. Polymère selon l'une quelconque revendication précédente, dans lequel les ramifications trifonctionnelles à longue chaîne se produisent à une fréquence d'au moins 0,05 pour 1 000 atomes de carbone, tel que déterminé par RMN.
  10. Polymère selon l'une quelconque revendication précédente, dans lequel les ramifications trifonctionnelles à longue chaîne se produisent à une fréquence d'au moins 0,1 pour 1 000 atomes de carbone, tel que déterminé par RMN.
  11. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a une résistance à l'état fondu supérieure à 6 cN, telle que mesurée par dispositif Rheotens, 190 °C, 2,4 mm/s2, 120 mm de la sortie de filière au centre des roues, taux d'extrusion de 38,2 s-1, filière capillaire de 30 mm de long, 2 mm de diamètre et angle d'entrée de 180°.
  12. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a une masse moléculaire moyenne en poids (Mw) inférieure ou égale à 800 000 daltons, telle que déterminée par chromatographie par perméation de gel à l'aide d'un triple détecteur.
  13. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a une masse moléculaire moyenne en poids (Mw) inférieure ou égale à 400 000 daltons, telle que déterminée par chromatographie par perméation de gel à l'aide d'un triple détecteur.
  14. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a une masse moléculaire moyenne en poids (Mw) inférieure ou égale à 200 000 daltons, telle que déterminée par chromatographie par perméation de gel à l'aide d'un triple détecteur.
  15. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a une masse moléculaire moyenne en poids (Mw) inférieure à 150 000 daltons, telle que déterminée par chromatographie par perméation de gel à l'aide d'un triple détecteur.
  16. Polymère selon l'une quelconque revendication précédente, dans lequel le polymère a une masse moléculaire moyenne en poids/masse moléculaire moyenne en nombre, Mw/Mn, inférieure à 4, telle que déterminée par chromatographie par perméation de gel à l'aide d'un triple détecteur.
EP20721035.2A 2019-03-29 2020-03-27 Polyoléfine ramifiée à longue chaîne trifonctionnelle Active EP3947484B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962826274P 2019-03-29 2019-03-29
PCT/US2020/025387 WO2020205585A1 (fr) 2019-03-29 2020-03-27 Polyoléfine ramifiée à longue chaîne trifonctionnelle

Publications (2)

Publication Number Publication Date
EP3947484A1 EP3947484A1 (fr) 2022-02-09
EP3947484B1 true EP3947484B1 (fr) 2025-04-23

Family

ID=70416549

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20721035.2A Active EP3947484B1 (fr) 2019-03-29 2020-03-27 Polyoléfine ramifiée à longue chaîne trifonctionnelle

Country Status (8)

Country Link
US (1) US12065523B2 (fr)
EP (1) EP3947484B1 (fr)
JP (2) JP7534321B2 (fr)
KR (1) KR20210149083A (fr)
CN (1) CN113614126B (fr)
ES (1) ES3032837T3 (fr)
SG (1) SG11202109338WA (fr)
WO (1) WO2020205585A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112022018394A2 (pt) 2020-03-27 2022-11-08 Dow Global Technologies Llc Polímero à base de etileno
US12479937B2 (en) 2020-03-27 2025-11-25 Dow Global Technologies Llc Process for producing long-chain branched ethylene-based polymers
US12497472B2 (en) 2020-03-27 2025-12-16 Dow Global Technologies Llc Long-chain branched ethylene-based polymers
WO2025006179A1 (fr) 2023-06-28 2025-01-02 Dow Global Technologies Llc Polymères à base d'éthylène trimodaux
WO2025006180A1 (fr) 2023-06-28 2025-01-02 Dow Global Technologies Llc Processus de fabrication de polymères multimodaux à base d'éthylène
WO2025006178A1 (fr) 2023-06-28 2025-01-02 Dow Global Technologies Llc Films polymères ayant une combinaison supérieure de capacité de traitement et de résistance à l'utilisation incorrecte
WO2025049300A1 (fr) 2023-08-28 2025-03-06 Dow Global Technologies Llc Mélanges polymères comprenant des polymères trimodaux à base d'éthylène et un pcr
WO2025049301A1 (fr) 2023-08-28 2025-03-06 Dow Global Technologies Llc Mélanges de polymères comprenant des polymères à base d'éthylène recyclé post-consommation (pcr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994000500A1 (fr) * 1992-06-26 1994-01-06 Exxon Chemical Patents Inc. Procede de polymerisation en solution utilisant un catalyseur metallocene pour la production de polymeres olefiniques

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4928993A (en) * 1992-09-29 1994-04-26 Exxon Chemical Patents Inc. Long chain branched polymers and a process to make long chain branched polymers
JPH0859723A (ja) * 1994-08-17 1996-03-05 Showa Denko Kk エチレン系重合体およびその製造方法
US6300451B1 (en) * 1994-10-24 2001-10-09 Exxon Chemical Patents Inc. Long-chain branched polymers and their production
US5965756A (en) 1996-12-19 1999-10-12 The Dow Chemical Company Fused ring substituted indenyl metal complexes and polymerization process
US6355757B2 (en) * 1997-02-14 2002-03-12 Exxonmobil Chemical Patents, Inc. Processing olefin copolymers
ES2317834T3 (es) * 1999-05-05 2009-05-01 Ineos Europe Limited Copolimeros de etileno y peliculas elaboradas con los mismos.
KR100387734B1 (ko) 2000-06-17 2003-06-18 삼성종합화학주식회사 올레핀 중합용 촉매 및 중합방법
US20040241130A1 (en) 2002-09-13 2004-12-02 Krishnan Tamareselvy Multi-purpose polymers, methods and compositions
EP3009459B1 (fr) 2004-06-16 2017-08-02 Dow Global Technologies LLC Procédé de polymérisation d'oléfine employant un modificateur
CN101035813A (zh) * 2004-07-01 2007-09-12 宾夕法尼亚州研究基金会 用于制备长支链聚合物的一锅法和试剂
US7713907B2 (en) 2006-03-06 2010-05-11 Uchicago Argonne, Llc Method of preparing size-selected metal clusters
TWI427114B (zh) * 2008-05-09 2014-02-21 Tosoh Corp 聚乙烯樹脂組成物及由此構成的積層體
CA2789571A1 (fr) * 2010-02-12 2011-08-18 Rhodia Operations Polymere modificateur de rheologie
US9321911B2 (en) 2011-09-23 2016-04-26 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions for cast film
JP5960831B2 (ja) 2011-09-23 2016-08-02 エクソンモービル ケミカル パテンツ インコーポレイテッド 改質ポリエチレン組成物
JP5810880B2 (ja) 2011-12-13 2015-11-11 東ソー株式会社 エチレン系重合体およびその製造方法
ES3037846T3 (en) 2018-09-28 2025-10-07 Dow Global Technologies Llc Tetra-functional long-chain branched ethylene-based polymers
EP3856804A1 (fr) 2018-09-28 2021-08-04 Dow Global Technologies LLC Procédé de polymérisation de résines de polyoléfines ramifiées à longue chaîne tétrafonctionnelles
US11926685B2 (en) * 2018-09-28 2024-03-12 Dow Global Technologies Llc Tetra-functional long-chain branched ethylene-based polymers
KR102834311B1 (ko) * 2018-09-28 2025-07-17 다우 글로벌 테크놀로지스 엘엘씨 4작용성 장쇄 분지형 에틸렌계 중합체

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994000500A1 (fr) * 1992-06-26 1994-01-06 Exxon Chemical Patents Inc. Procede de polymerisation en solution utilisant un catalyseur metallocene pour la production de polymeres olefiniques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ERIC J MARKEL ET AL: "Metallocene-Based Branch-Block Thermoplastic Elastomers", vol. 33, no. 23, 1 January 2000 (2000-01-01), pages 8541 - 8548, XP002682460, ISSN: 0024-9297, Retrieved from the Internet <URL:http://pubs.acs.org/doi/abs/10.1021/ma001087b> [retrieved on 20001028], DOI: 10.1021/MA001087B *

Also Published As

Publication number Publication date
JP2024156836A (ja) 2024-11-06
KR20210149083A (ko) 2021-12-08
JP7534321B2 (ja) 2024-08-14
SG11202109338WA (en) 2021-09-29
BR112021018779A2 (pt) 2021-11-23
CN113614126B (zh) 2023-12-01
JP2022528489A (ja) 2022-06-13
US20220227905A1 (en) 2022-07-21
US12065523B2 (en) 2024-08-20
WO2020205585A1 (fr) 2020-10-08
ES3032837T3 (en) 2025-07-28
CN113614126A (zh) 2021-11-05
JP7737521B2 (ja) 2025-09-10
EP3947484A1 (fr) 2022-02-09

Similar Documents

Publication Publication Date Title
EP3947484B1 (fr) Polyoléfine ramifiée à longue chaîne trifonctionnelle
EP3856805B1 (fr) Polymères ramifiés à longue chaîne tétrafonctionnels à base d&#39;éthylène
EP3856803B1 (fr) Polymères à base d&#39;éthylène ramifiés à longue chaîne tétra-fonctionnels
EP3856802B1 (fr) Polymères à base d&#39;éthylène ramifiés à longue chaîne tétra-fonctionnels
US12077619B2 (en) Process of polymerizing tetra-functional long-chain branched polyolefin resins
US20220213246A1 (en) Process of polymerizing tri-functional long-chain branched olefin
US20220169761A1 (en) Process of polymerizing tri-functional long-chain branched olefin
KR102900558B1 (ko) 4작용성 장쇄 분지형 폴리올레핀 수지를 중합하는 방법

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210929

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230526

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20241129

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602020049920

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 3032837

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20250728

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1787718

Country of ref document: AT

Kind code of ref document: T

Effective date: 20250423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250423

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250825

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250724

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250723

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250723

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250423